The strive toward sustainability increases the demand for bio-based material production, forcing expansion of the biorefinery feedstock supply from forest wood to non-woody materials such as agricultural residues. As a model organism for legume crops, the aptness of agricultural lupins as a lignocellulose feedstock is investigated. Principle chemical analysis combined with optotracing, in which the fluorescent tracer molecule Carbotrace 680 generates a visual map of the native tissues’ lignocellulose anatomy at sub-cellular resolution, enables informed design of a mild recovery process. A streamlined conversion approach is then designed, yielding lignin-containing microfibrillated cellulose. By monitoring defibrillation and delignification throughout the extraction process, the use of optotracing for non-destructive fiber analytics at unprecedented details across all hierarchical structures of lignocellulosic materials is demonstrated. This crop valorization is a prime illustration of a holistic use of lupin biomass, with seeds serving as plant-based food sources, and other parts as sources for lignocellulose-based materials, thereby expanding both the biorefinery concept and feedstock supply.

The oxidation of cellulose to dialdehyde cellulose (DAC) is a process that has received increased interest during recent years. Herein, kinetic modeling of the reaction with sodium periodate as an oxidizing agent was performed to quantify rate-limiting steps and overall kinetics of the cellulose oxidation reaction. Considering a pseudo-first-order reaction, a general rate expression was derived to elucidate the impact of pH, periodate concentration, and temperature on the oxidation of cellulose and concurrent formation of cellulose degradation products. Experimental concentration profiles were utilized to determine the rate constants for the formation of DAC (k1), degradation constant of cellulose (k2), and degradation of DAC (k3), confirming that the oxidation follows a pseudo-first-order reaction. Notably, the increase in temperature has a more pronounced effect on k1 compared to the influence of IO4− concentration. In contrast, k2 and k3 display minimal changes in response to IO4− concentration but increase significantly with increasing temperature. The kinetic model developed may help with understanding the rate-limiting steps and overall kinetics of the cellulose oxidation reaction, providing valuable information for optimizing the process toward a faster reaction with higher yield of the target product.

The search for new energy sources together with the need to control greenhouse gas emissions has led to continued interest in low-emitting renewable energy technologies. In this context, water splitting for hydrogen production is a reasonable alternative to replace fossil fuels due to its high energy density producing only water during combustion. Cellulose is abundant in nature and as residuals from human activity, and therefore a natural, ecological, and carbon-neutral source for hydrogen production. In the present work, we propose a sustainable method for hydrogen production using sunlight and cellulose as sacrificial agents during the photocatalytic water splitting process. Platinum (Pt) catalyst activates hydrogen production, and parameters such as pH of the system, cellulose concentration, and Pt loading were studied. Using different biomasses, we found that the presence of hemicellulose and xyloglucan as part of the molecular composition considerably increased the H-2 production rate from 36 mu mol L-1 in one hour for rapeseed cellulose to 167.44 mu mol L-1 for acid-treated cellulose isolated from Ulva fenestrata algae. Carboxymethylation and TEMPO-oxidation of cellulosic biomass both led to more stable suspensions with higher rates of H-2 production close to 225 mu mol L-1, which was associated with their water solubility properties. The results suggest that cellulosic biomass can be an attractive alternative as a sacrificial agent for the photocatalytic splitting of water for H-2 production.

The production and engineering of sustainable materials through green chemistry will have a major role in our mission of transitioning to a more sustainable society. Here, combined catalysis, which is the integration of two or more catalytic cycles or activation modes, provides innovative chemical reactions and material properties efficiently, whereas the single catalytic cycle or activation mode alone fails in promoting a successful reaction. Polyphenolic lignin with its distinctive structural functions acts as an important template to create materials with versatile properties, such as being tough, antimicrobial, self-healing, adhesive, and environmentally adaptable. Sustainable lignin-based materials are generated by merging the catalytic cycle of the quinone-catechol redox reaction with free radical polymerization or oxidative decarboxylation reaction, which explores a wide range of metallic nanoparticles and metal ions as the catalysts. In this review, we present the recent work on engineering lignin-based multifunctional materials devised through combined catalysis. Despite the fruitful employment of this concept to material design and the fact that engineering has provided multifaceted materials able to solve a broad spectrum of challenges, we envision further exploration and expansion of this important concept in material science beyond the catalytic processes mentioned above. This could be accomplished by taking inspiration from organic synthesis where this concept has been successfully developed and implemented.

Stimuli-responsive materials with reversible supramolecular networks controlled by a change in temperature are of interest in medicine, biomedicine and analytical chemistry. For these materials to become more impactful, the development of greener synthetic practices with more sustainable solvents, lower energy consumption and a reduction in metallic catalysts is needed. In this work, we investigate the polymerisation of N-acryloyl glycinamide monomer by single-electron transfer reversible-deactivation radical polymerisation and its effect on the cloud point of the resulting PNAGA polymers. We accomplished 80% conversion within 5 min in water media using a copper wire catalyst. The material exhibited a sharp upper critical solution temperature (UCST) phase transition (10–80% transition within 6 K). These results indicate that UCST-exhibiting PNAGA can be synthesized at ambient temperatures and under non-inert conditions, eliminating the cost- and energy-consuming deoxygenation step. The choice of copper wire as the catalyst allows the possibility of catalyst recycling. Furthermore, we show that the reaction is feasible in a simple vial which would facilitate upscaling.

The sustainable production of polymers and materials derived from renewable feedstocks such as biomass is vital to addressing the current climate and environmental challenges. In particular, finding a replacement for current widely used curable resins containing undesired components with both health and environmental issues, such as bisphenol-A and styrene, is of great interest and vital for a sustainable society. In this work, we disclose the preparation and fabrication of an all-biobased curable resin. The devised resin consists of a polyester component based on fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and reactive diluents acting as both solvents and viscosity enhancers. Importantly, the complete process was performed solvent-free, thus promoting its industrial applications. The cured biobased resin demonstrates very good thermal properties (stable up to 415 °C), the ability to resist deformation based on the high Young’s modulus of ∼775 MPa, and chemical resistance based on the swelling index and gel content. We envision the disclosed biobased resin having tailorable properties suitable for industrial applications.

Biobased adsorbents and membranes offer advantages related to resource efficiency, safety, and fast kinetics but have challenges related to their reusability and water flux. Nanocellulose/alginate composite hydrogel beads were successfully prepared with a diameter of about 3-4 mm and porosity as high as 99%. The beads were further modified with in situ TEMPO-mediated oxidation to functionalize the hydroxyl groups of cellulose and facilitate the removal of cationic pollutants from aqueous samples at low pressure, driven by electrostatic interactions. The increased number of carboxyl groups in the bead matrix improved the removal efficiency of the adsorbent without compromising the water throughput rate; being as high as 17 000 L h(-1) m(-2) bar(-1). The absorptivity of the beads was evaluated with UV-vis for the removal of the dye Methylene Blue (91% removal) from spiked water and energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) elemental analyses for the removal of Cd2+ from industrial mining effluents. The modified beads showed a 3-fold increase in ion adsorption and pose as excellent candidates for the manufacturing of three-dimensional (3-D) column filters for large-volume, high flux water treatment under atmospheric pressure.

The seaweed Saccharina latissima is often blanched to lower iodine levels, however, it is not known how blanching affects protein extraction. We assessed the effect of blanching or soaking (80/45/12 degrees C, 2 min) on protein yield and protein extract characteristics after pH-shift processing of S. latissima. Average protein yields and extract amino acid levels ranked treatments as follows: blanching-45 degrees C -control > soaking -blanching -80 degrees C. Although blanching-45 degrees C decreased protein solubilization yield at pH 12, it increased isoelectric protein precipitation yield at pH 2 (p < 0.05). The former could be explained by a higher ratio of large peptides/proteins in the blanched biomass as shown by HP -SEC, whereas the latter by blanching-induced lowering of ionic strength, as verified by a dialysis model. Moreover, blanching-45 degrees C yielded a protein extract with 49 % less iodine compared with the control extract. We recommend blanching-45 degrees C since it is effective at removing iodine and does not compromise total protein extraction yield.

Climate change is causing unprecedented changes in terrestrial and aquatic ecosystems through the emission of greenhouse gases, including carbon dioxide (CO2). Approximately 30% of CO2 is taken up by the ocean (‘ocean acidification’, OA)1, which has profound effects on foundation seaweed species. Negative physical effects on calcifying algae are clear2, but studies on habitat-forming fleshy seaweeds have mainly focused on growth and less on thallus strength3,4. We exposed the habitat-forming brown seaweed Fucus vesiculosus to OA corresponding to projected climate change effects for the year 2100, and observed reduced apical thallus strength and greater loss of exposed individuals in the field. The tissue contained less calcium and magnesium, both of which are important for creating structural alginate matrices. Scanning electron microscopy (SEM) revealed tissue voids in the OA samples that were not present in seaweeds grown under ambient pCO2. We conclude that under OA, weakened F. vesiculosus will be at a significantly higher risk of physical damage and detachment.

Inhomogeneous lignin from a canola (rapeseed) straw was isolated and valorized as regularly shaped spherical microparticles for drug delivery formulations. Lignin with a purity of 83% and broad molecular weight distribution (<SIC> > 5.0) was extracted by alkali pulping and acetylated to increase spheronization ability. Lignins with high degrees of acetylation (0.76 and 0.89) were successfully assembled into microparticles with uniform sizes (approximately 2 mu m) and smooth spherical surfaces via solvent-antisolvent precipitation. Hydrophobic coumarin 153 and positively charged ciprofloxacin were used as model drugs to assess the encapsulation and release performance of lignin microparticles. Highly acetylated lignin microparticles displayed encapsulation efficiencies of 89.6% for coumarin 153% and 90.6% for ciprofloxacin. Scanning electron microscope images showed that coumarin 153 was encapsulated in the hydrophobic core, while ciprofloxacin was adsorbed on the less hydrophobic shell. The synthesis of lignin microcarriers not only provides a facile approach to utilizing waste canola straw lignin for drug delivery matrices but also has the potential to serve as an alternative lignin powder feedstock for bio-based materials.